CN101304943B - Hydrogen generating agent and use thereof - Google Patents
Hydrogen generating agent and use thereof Download PDFInfo
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- CN101304943B CN101304943B CN2006800416646A CN200680041664A CN101304943B CN 101304943 B CN101304943 B CN 101304943B CN 2006800416646 A CN2006800416646 A CN 2006800416646A CN 200680041664 A CN200680041664 A CN 200680041664A CN 101304943 B CN101304943 B CN 101304943B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/22—Gas releasing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention provides a hydrogen-generating agent which comprises a hydrogen compound, such as an alkali metal hydride, alkaline earth metal hydride, or metal salt of boron hydride, and a solid water-soluble compound such as polyethylene glycol or an organic acid, the hydrogen compound being embedded in the water-soluble compound. It is easy to handle. This hydrogen-generating agent slowly generates hydrogen while dissolving in water. The water in which the hydrogen-generating agent has been dissolved has an oxidation/reduction potential reduced considerably to the reduction side. The hydrogen-generating agent is hence utilizable for regulating a reducing cosmetic preparation, beverage, or bath water. The hydrogen generated is utilizable as a fuel for fuel cells.
Description
Technical field
The present invention relates to use the hydrogen generating agent of metal hydride or hydroboration metal-salt; And through making itself and water reaction produce hydrogen; And thus hydrogen is dissolved in the purposes for preparing cosmetic with reductibility, beverage, bath water etc. in the waterborne compositions, and the hydrogen that generates is used as the fuel of fuel cell.
Background technology
Known with hydrogen when water-soluble, the redox potential of water (being designated hereinafter simply as ORP) reduces in reduction one side.Existing report; Because this reductive water or reductibility waterborne compositions have antioxygenation, if therefore drink, thereby then eliminate activity oxygen helps physiological well-being; If perhaps be used for skincare products such as astringent, then have the effect (patent documentation 1) that prevents skin aging.In addition, the reductive water that carbonic acid gas is dissolved in bath water through using is also disclosed, thus the technology (patent documentation 2) that expectation simultaneously prevents skin aging and stimulates circulation.
As the technology that generates hydrogen, the above-mentioned effect of expectation is disclosed, make the reaction of MAGNESIUM METAL 99 and water, generate the technology (patent documentation 3) that hydrogen prepares reductive water.In addition; The hydrogen supply source that the battery that acts as a fuel is used; Disclose through the water-repellancy barrier film make the reaction of hydrolith and water vapour technology (patent documentation 4), make alkaline-earth metal hydrogenate and technology (patent documentation 5) by acid and the formed solution reaction of water; Or thermoplastic resin powders such as the powder of hydroboration metal-salt etc. and Vilaterm are mixed and be shaped to the compressed moulding body; And the surface of one side cutting forming body makes itself and the reaction of tart water on one side, thereby the technology (patent documentation 6) of generation hydrogen etc.
Patent documentation 1: TOHKEMY 2000-119161 communique
Patent documentation 2: TOHKEMY 2000-308891 communique
Patent documentation 3: TOHKEMY 2004-041949 communique
Patent documentation 4: TOHKEMY 2004-269323 communique
Patent documentation 5: TOHKEMY 2002-080201 communique
Patent documentation 6: TOHKEMY 2003-146604 communique
Summary of the invention
The problem that invention will solve
Though present inventors etc. consider that the solubleness of hydrogen in water is very little; Thereby, this few dissolved hydrogen generates reductive water but making the ORP of water reduce greatly in reduction one side; And then; The hydrogen that is conceived to generate can be as the fuel of fuel cell, and consideration and water reaction generate the exploitation of the hydrogen generating agent of hydrogen.
As generating the material of hydrogen, known just like being the hydrogenation alkaline-earth metal of representative, being the hydroboration metal-salt etc. of representative with the Peng Qinghuana described in the background technology with magnesium metal, magnesium hydride with water reaction.Magnesium metal and water or the reaction of tart water generate hydrogen, but speed of response is slow, and be therefore impracticable.Because the hydrogen generating agent that magnesium hydride or Peng Qinghuana are also used as fuel cell therefore in order to improve speed of response, needs tart water.In addition, because these hydrogen compounds are in order to improve speed of response but micronized and have water absorbability, so difficult treatment.
On the other hand, owing to being swift in response of hydrolith and lithium hydride and water, when contacting with water, moment reacts and generates hydrogen, therefore can't use with original state.In addition, when making the reaction of Peng Qinghuana and tart water, speed of response is also very fast, is difficult to control the formation speed of hydrogen.Problem of the present invention is to suppress speed of response this and the willing hydrogen compound of water, and a kind of hydrogen generating agent of practicality is provided.In addition, even a kind of hydrogen compound that in hydrogen generates, needs sour water also is provided, also can generate the hydrogen generating agent of hydrogen through using neutral water.Further, a kind of easy to handle hydrogen generating agent is provided.
The means of dealing with problems
The problems referred to above solve through the hydrogen generating agent with following characteristic: this hydrogen generating agent is embedded in through at least a hydrogen compound that will be selected from hydrogenated alkali metal, hydrogenation alkaline-earth metal, hydroboration metal-salt in water-soluble cpds or their mixture of solid-like and forms.Wherein the preferably water soluble compound is a macromolecular compound, more preferably the hydrogen generating agent of polyoxyethylene glycol.In addition, preferably in the mixture of water-soluble cpds, contain acid and the hydrogen generating agent that forms.Further, preferably these hydrogen generating agents form through being shaped to the tablet shape.
As the purposes of these hydrogen generating agents, provide and contained the bath shampoo of hydrogen generating agent as constituent.In addition, through water-soluble or waterborne compositions, can obtain reductive water or reductibility waterborne compositions with these hydrogen generating agents.Therefore, provide through making the reaction of these hydrogen generating agents and water or waterborne compositions generate the method for forming hydrogen of hydrogen.
The invention effect
Through hydrogen compounds such as hydrolith, lithium hydride, Peng Qinghuana being embedded in the solid-like water-soluble cpdss such as polyoxyethylene glycol, the sluggish of these hydrogen compounds and water or sour water is carried out.In addition, through in water-soluble cpds, containing the acid of solid-like, can use hydrogen compounds such as magnesium hydride or Peng Qinghuana to be dissolved in the neutral water, and generate hydrogen effectively.
Hydrogen generating agent of the present invention owing to can be shaped to form arbitrarily such as tablet shape, bulk, particulate state, granular, powder shaped, is therefore handled easily.Through hydrogen generating agent of the present invention is dissolved in cosmetic or tap water, perhaps, can give these waterborne compositions reductibilities at an easy rate as bath shampoo.
Embodiment
As hydrogenated alkali metal used among the present invention, lithium hydride (LiH), sodium hydride (NaH), potassium hydride KH (KH) etc. are arranged for example.Wherein, because LiH is more stable in air, be preferred compound therefore.In addition, as the hydrogenation alkaline-earth metal, magnesium hydride (MgH2), hydrolith (CaH2), barium hydride (BaH2), beryllium hydride (BeH2), hydrogenation strontium (SrH2) etc. are arranged for example.Wherein, because MgH2, CaH2 are more stable in air, be preferred compound therefore.
Hydroboration metal-salt used among the present invention is represented by formula M BH4.M is a basic metal, and lithium, sodium, potassium, rubidium are arranged for example.In these metal-salts, sodium salt (Peng Qinghuana, abbreviate later on SBH) is in security and preferred in price.These hydrogen compounds can use separately, also can mix use.
Hydrogenated alkali metal (MH) and water reaction generate hydrogen shown in Chemical formula 1 (M is a basic metal).
[changing 1]
MH+H
2O→H
2+M(OH)
The reaction of hydrogenation alkaline-earth metal and water is shown in Chemical formula 2 (M is an alkaline-earth metal), and the reaction of hydroborons metal-salt (M is a basic metal) and water generates hydrogen shown in chemical formula 3.
[changing 2]
MH
2+2H
2O→2H
2+M(OH)
2
[changing 3]
MBH
4+2H
2O→4H
2+MBO
2
Present inventors etc. think, through making the hydrogen that generates in these reactions soluble in water, the ORP of water are reduced, and form reductive water.Yet; When LiH or CaH2 contact with water; Therefore be the intense reaction that reacts such moment, with CaH2 powder (commercially available CaH2 is the fine powdered of the microparticle agglutination of submicron when using microscopic examination) when being added into the water surface; Intense reaction, and arrived powder and disperse to airborne degree.
Therefore, expect hydrogen compound is embedded in the water-soluble cpds of solid-like, so that when this hydrogen compound that carries out with the reaction fierceness of water contacted with water, this sluggish was carried out.That is, expect through in water-soluble cpds, wrapping into hydrogen compound, thereby when contacting with water, water-soluble cpds at first dissolves, then the technology of hydrogen compound such as the CaH2 of institute's embedding and water reaction wherein.Be astoundingly, this idea is confirmed fully, only is dispersed in simply in the water-soluble cpds through the powder with hydrogen compound and solidifies, and the reaction with water is relaxed, and the hydrogen of generation is dissolved in the water effectively.Simultaneously, because hydrogen also slowly generates, therefore expectation can be as the fuel of fuel cell.
On the other hand, in hydrogen compound, MgH2 or hydroboration metal-salt speed of response in neutral water slowly or is hardly reacted.For head it off; Discoveries such as present inventor through when being dispersed in these hydrogen compounds in the water-soluble cpds and solidifying, use the acid of solid-like to prepare hydrogen generating agent as water-soluble cpds; Even then be dissolved in the neutral water, also can effectively generate hydrogen.
So-called water-soluble cpds among the present invention, so long as at room temperature be solid matter, and water-soluble material gets final product.In addition, can be single component, also can be mixing element, and can be macromolecular compound, also can be low molecular compound.As macromolecular compound, be water-soluble polymer, polyoxyethylene glycol (after, abbreviate PEG as), Z 150PH, Vinylpyrrolidone polymer, SEPIGEL 305, ROHM, polymethyl acrylic acid or their synthetic macromolecules such as salt are arranged for example.As natural polymer, starch, dextrin, X 5189 are arranged for example, more create glue, XG 550 etc.In addition, as semi-synthetic polymer, derivatived celluloses such as methylcellulose gum, hydroxyethylmethyl-cellulose, Vltra tears, carboxy methyl cellulose or its salt are arranged for example.
As low molecular compound; Oligosaccharides or Schardinger dextrins such as monoses such as wood sugar, Xylitol, glucose, sorbitol, fructose, seminose, sucrose, SANMALT-S, trehalose, raffinose are arranged for example; And, at high temperature fusion monose or oligosaccharides and amino acid such as the caramel shape thing for preparing, L-glutamic acid, asparagus fern amino acid or its salt etc.In addition, inorganic salt such as carbonate such as sodium hydrogencarbonate, yellow soda ash, sodium-chlor, sodium sulfate, SODIUMNITRATE, Sodium Tetraborate are also arranged for example.In these water-soluble cpdss, macromolecular compound, particularly PEG since after state reason, therefore be preferred embedding medium.In addition, in low molecular compound, organic cpds is preferred embedding medium.
For with the effectively soluble in water and preparation reductibility waterborne compositions of hydrogen, hydrogen generating agent preferably reacts with water with the state that sinks in the water.Therefore, when the embedding hydrogen compound, preferably with heavy inorganic salt for example sodium sulfate etc. be mixed in the water-soluble cpds as additive.
On the other hand, because hydrogen compound shown in Chemical formula 1 or 2 and water reaction generate metal hydroxides, the waterborne compositions that therefore dissolves them becomes alkalescence.Therefore, when wanting the neutral or weakly acidic reductibility waterborne compositions of preparation, preferred mixing acid in water-soluble cpds.In addition, under the situation of hydrogen compounds such as MgH2 or SBH, in order to promote reaction, acid is necessary.At this moment, preferably in water-soluble cpds mixing acid prepare hydrogen generating agent.
As acid, be solid-like acid, can be single component, also can be mixing element.As organic acid, carboxylic acids such as fumaric acid, toxilic acid, maleic anhydride, succsinic acid, succinyl oxide, tartrate, oxysuccinic acid, Hydrocerol A, oxalic acid, propanedioic acid, xitix and amino acid such as polymeric carboxylics such as various verivate or ROHM, polymethyl acrylic acid, L-glutamic acid thereof are arranged for example.As mineral acid, thionamic acid, boric acid, metaboric acid, boron oxide etc. are arranged for example.
The amount of blended acid in water-soluble cpds, when wanting to obtain neutral reductibility waterborne compositions, so long as in and the amount of the alkali that in hydrogen compound and water react, generated get final product.Dosis neutralisata like the combined amount of tartaric acid and alkali is different, and then the reductibility waterborne compositions becomes slightly acidic or weakly alkaline, thereby can prepare such reducing composition.In addition, under the situation of the such hydrogen compound of MgH2 or SBH, because acidity is strong more, the formation speed of hydrogen is fast more, and therefore can make the combined amount of acid as required is more than the neutralization bases.Even contain the hydrogen generating agent of the acid of dosis neutralisata, when considering with its process soluble in water, the pH of imagination hydrogen generating agent dissolving part, the pH more whole than whole dissolvings neutralizations and the water accomplished is low.Therefore, compare, can think that it effectively generates hydrogen (referring to the example of the MgH2 of embodiment 26) with the situation that directly hydrogen compound is dissolved in the sour water that has added dosis neutralisata acid.
So-called embedding among the present invention representes that pulverous hydrogen compound disperses the state in the water-soluble cpds that remains on.The embedding mode preferably, the powder of hydrogen compound disperses to remain on the marine state of water-soluble cpds with the form on island.The ratio on sea and island is by the mixture ratio control of hydrogen compound and water-soluble cpds.Mixture ratio preferably makes hydrogen compound with 0.1～50 quality %, and more preferably the scope with 0.5～30 quality % is included in the water-soluble cpds.When amount is 0.1 quality % when following, the growing amount of hydrogen is few, need hydrogen generating agent of the present invention is soluble in water in a large number, and therefore not preferred.In addition, when it surpassed 50 quality %, the powder of hydrogen compound was not dispersed in the water-soluble cpds with island, and became many with state of aggregation dispersive zone, and the reaction of hydrogen generating agent and water accelerates, and is therefore not preferred.
Then, for the method that will use water-soluble cpds embedding hydrogen compound powder 2,3, describe hereinafter.No matter under the situation of which kind of method of employing, all preferably will dehydrate as the water-soluble cpds of embedding medium in advance and use.This be because, even moisture is with minimal residue, because hydrogen compound and this reaction of moisture, so a large amount of inactivations of the hydrogen compound in the hydrogen generating agent of gained.
The 1st embedding method is the fusion entrapping method.The crystallinity water-soluble cpds that will have fusing point is heated to and makes its fusion more than the fusing point, and interpolation hydrogen compound powder also mixes, and needs, and further adds powder acid or inorganic salt etc., it is dispersed in the molten mass, cooling curing.Since molecular weight be PEG 1000 or more at room temperature for solid-like, and fusing point is low to moderate near 65 ℃, so as the water-soluble cpds of embedding hydrogen compound powder, is preferred compound.Because the PEG melt viscosity that molecular weight is high is high, therefore preferably use the PEG below 20,000.
If use this macromolecular compound, then can use suitable shaped device, be pencil with the melts extrusion moulding that is mixed with hydrogen compound.In addition, can be suitable length with tractotomy, and be shaped to granular hydrogen generating agent.And being easy to through suitable kibbler is the form of granular or powder shaped with grain forming.And,, can be shaped to the block or the club of any form at an easy rate through melts being injected suitable mold.
The 2nd embedding method is the solution entrapping method.With water-soluble cpds be dissolved in the nonreactive organic solvent of hydrogen compound in prepare solution, add the hydrogen compound powder, mix, form mixing solutions, and in suitable shaped device, be shaped to film like or fibrous etc., dry removing desolvated.Or, when water-soluble cpds is macromolecular compound, with mixing solutions put into the nonreactive high molecular non-solvent of hydrogen compound in, and make polymer deposition with the form that comprises hydrogen compound, make the method for drying precipitate then.Because the 2nd method is with an organic solvent, therefore must carry out dehydrating of solvent, and carrying capacity of environment is big, from this meaning, preferred the 1st fusion entrapping method.
The 3rd embedding method is an extrusion forming method.With pulverous hydrogen compound and powder or granulous water-soluble cpds uniform mixing, and use suitable pressure forming machine to be shaped to particulate state or tablet shape.In the method, for the powder that makes hydrogen compound disperses to remain in the water-soluble cpds securely, the preferred water-soluble cpds that demonstrates the wedding agent effect that uses preferably uses aforesaid macromolecular compound or organic cpds as embedding medium.In addition, the pressure during extrusion forming is preferably the scope of 0.5～20 ton/cm2, if pressure is low; Then forming composition is because moisture absorption etc. and collapse easily is therefore not preferred, and if pressure high; Then dissolution time in water or hydrogen rise time are elongated, therefore not preferred.
The size of forming composition, can be when being chosen in moulding the grip size of powder filler, and moulding number millimeter object to the number cm sizes.This extrusion forming method needs the mixed processes and these 2 operations of pressurization operation of powder, but compares with aforesaid fusion entrapping method, does not have heat-processed, does not therefore have pyrolysated to worry for mixing element.Therefore, in the manufacturing of the hydrogen generating agent that contains this composition, be preferable methods.
Can also hydrogen generating agent that use the preparation of fusion entrapping method or solution entrapping method be pulverized and form powder and mixes as other powder shaped water-soluble cpds of additive, and be shaped to the tablet shape through extrusion forming method.In the method, additive can not be exposed in the entrapping method in employed heat or the organic solvent, in the preparation that contains this hydrogen generating agent that is prone to additive affected by environment, is preferable methods therefore.
Then, describe for the method for using hydrogen generating agent of the present invention to prepare reductive water or reductibility waterborne compositions (after, comprise water, be also referred to as the reductibility waterborne compositions).The ORP of tap water (among the present invention, ORP is the standard electrode benchmark, and representes its unit with mV) is shown as about about 800mV, and the ORP of purified water (having carried out the tap water that gac+ion exchange resin+secondary filter is handled) is shown as about about 400.In addition, known pH uprises, and then ORP reduces.So-called reductibility waterborne compositions among the present invention is when comparing with identical pH, demonstrates the waterborne compositions of the ORP lower than purified water ORP.Of embodiment, the hydrogen compound that only will count ppm is dissolved in tap water or the purified water, promptly can prepare the reductibility waterborne compositions.
So-called waterborne compositions among the present invention is aqueous compsn, preferably contains the compsn of the above water of 50 quality %.As the example of waterborne compositions, be cosmetic, the beverage that contains amino acid or mineral substance, bath water, washing composition etc. such as the water that contains acid or alkali, the astringent that contains various preserve moisture composition or whitening compositions, beauty liquid, emulsion, emulsifiable paste, gel Liniment.Through in these waterborne compositions, adding hydrogen generating agent of the present invention and making it water-soluble, can prepare the reductibility waterborne compositions at an easy rate.
The cosmetic that viscosity such as astringent are low under a lot of situation is and is filled in jointly in the aerosol jar as the nitrogen or the liquefied gas that spray with gas.At this moment, through in advance hydrogen generating agent of the present invention being packed in the aerosol can container, astringent injects in the side from it, and airtight with gas pressurization with injection, can make the astringent of reductibility at an easy rate.The aerosol can container is restriction not, as long as use hydrogen generating agent of the present invention, just can in the cosmetic container of end article, directly hydrogen be dissolved in cosmetic.Therefore, compare, have and to make no hydrogen dissipation, and kept the advantage of the cosmetic of high reductibility with the method for making of dissolving hydrogen in the pilot process of making.
In hydrogen generating agent of the present invention, do not contain under the situation of acid, when reacting with water, as previously mentioned, this reductibility waterborne compositions becomes alkalescence.Even though in the strong purposes that also it doesn't matter of alkalescence such as washing composition, do not have problems, in cosmetic etc., be preferably neutrality or slightly acidic under the more situation.In this purposes, in the reductibility waterborne compositions that becomes alkalescence, add acid, perhaps, complex acid in waterborne compositions and after becoming slightly acidic, add hydrogen generating agent and get final product.At this moment, can use aqueous acid, also can be mineral acid, but in this purposes that contacts with human body, preferred aforementioned various organic acids.
Weakly acidic Soda Ash Light 99.2min. has the effect that promotes cutaneous circulation, and is used for beverage, makeup or bath shampoo.Therefore, for the pH that makes the reductibility waterborne compositions is that slightly acidic or neutrality are used carbonic acid or carbonic acid gas, can prepare the reductibility waterborne compositions that contains carbonic acid.Because the reductibility waterborne compositions that contains carbonic acid gas is therefore preferred still to preventing more effective skin care use compsn such as skin aging.In addition, containing under MgH2 or SBH the hydrogen generating agent situation as hydrogen compound, owing to, can obtain above-mentioned skin care use compsn at an easy rate through using carbonic acid as tart water, therefore preferred.
When using carbonic acid to prepare weakly acidic reductibility waterborne compositions, can add before and after the hydrogen generating agent or simultaneously, add carbonic acid as acid.In addition,, can directly carbonic acid gas be dissolved in the waterborne compositions, also can it be dissolved in the waterborne compositions through carbonate or supercarbonate and organic acid reaction generation carbonic acid gas in order in waterborne compositions, to contain carbonic acid.In the latter case, can use these compounds are mixed as additive and hydrogen compound, and by the hydrogen generating agent of embedding medium embedding.When this hydrogen generating agent was dissolved in waterborne compositions, because hydrogen and carbonic acid gas generate simultaneously, therefore preferred adjustment carbonate or supercarbonate and organic acid content were so that the pH after the dissolving is slightly acidic.This hydrogen generating agent is preferably used as following bath shampoo.
Hydrogen generating agent of the present invention can be used as bath shampoo through being added into as particulate state or tablet shape in the bathtub.Shown in the embodiment of back, in tap water, only add the hydrogen compound of number mg/L, ORP just reduces hundreds of mv.Addition is many more, and then ORP is low more, but the preferred reductibility of bath water is the scope of-100～400mv.Because ORP can be used in the material deteriorations such as rubber of bathtub for the strong reducing property the below-100mv, and is therefore not preferred.In addition, when it is 400mv when above, because a little less than the reductibility, therefore not preferred.
If the addition of hydrogen compound is many, the concentration of the metal hydroxides that then generates uprises, and the pH of bath water is alkalescence.It is generally acknowledged that the pH that human body is suited is 4.5～10 scope.The adjustment of pH, organic acid that can be through will being used for the carbonic acid bath shampoo etc. is added into hydrogen generating agent as water-soluble cpds, prepares the bath shampoo with suitable pH.Because the characteristic of tap water changes according to the water source, therefore in order to make the pH after the bath shampoo dissolving constant, when the modulation bath shampoo, pH buffer reagent or regulator being added into hydrogen generating agent is preferable methods.
In bath shampoo, except that above-mentioned water-soluble cpds, can also add known additive.As these additives, fatty acid ester, Jojoba oil, Lipoval A, olive wet goods natural fats and oils etc. such as higher alcoholss such as dried orange peel, mentha leave, Stigma Croci, Flos Matricariae chamomillae, Rosmarinus officinalis etc. natural drug class, cetyl alcohol, Stearyl alcohol, glycerine, Sorbitol Powder and polyalcohols, lactic acid 14 esters, Isopropyl myristate, Wickenol 111 are arranged for example.
In addition, nonionogenic tensides such as USP Kosher fatty ester, propylene glycol fatty acid ester, cithrol, fungicidal preservative, metal chelator, pigment, spices etc. are arranged for example, but be not limited to this.In these compositions, though contain non-water-soluble oil component, they all are a small amount of interpolations the in the scope of not damaging effect of the present invention.These oil components are dispersed in the form blending in the water with emulsification, and preferred absorption blending is on water miscible porous metallic substance and be added in the bath shampoo.In addition, because the thermolysis easily mostly of these additives, so the preparation of bath shampoo, preferably carry out through the combination of extrusion forming method or fusion entrapping method and extrusion forming method.
When hydrogen generating agent of the present invention and water reaction,, generate hydrogen according to aforementioned Chemical formula 1～3.Though this hydrogen trace is soluble in water, and produce aforesaid reductibility waterborne compositions, most of dissipation from water.The hydrogen purity of this dissipation is high, can be used for various uses.One of them is the fuel that fuel cell is used.Fuel cell is to make the face-off of fuel electrodes and air pole through dielectric medium, to the fuel electrodes hydrogen supply, to air pole air supply or oxygen, and carries out that electronics is given and accepted on extremely and the object that generates electricity at each.Hydrogen as supplying with to this fuel electrodes can utilize hydrogen generating agent of the present invention.
If use hydrogen generating agent of the present invention,, just can generate hydrogen as long as water is arranged.In addition, because this hydrogen generating agent is embedded in the macromolecular compound etc., therefore safety and handling easily.For example, if container of having filled the powdery hydrogen generating agent and the container of having filled water are arranged, then can be assembled into small-sized hydrogen producing apparatus.In the charging purposes of the battery of portable phone or PC etc., need small-sized fuel cell, and in this purposes, be contemplated to the most suitable use hydrogen generating agent of the present invention.
Below use embodiment that the present invention is described in further detail, but technical scope of the present invention is not limited to these embodiment.In addition, ORP used among the embodiment measures, and uses ORP survey meter (east and chemistry institute (Toko Chemical Laboratories) manufactured) to carry out.It is the powder (SIGMA-ALDRICH manufactured) of 0～2mm of 90～95% that test portion CaH2 uses purity; LiH uses in mortar 1 grade of article; The block of purity min.98% (pure pharmaceutical worker already makes with light) is pulverized and is the material of powder; It is the powder of 98% (Alfa Aescar manufactured) that MgH2 uses purity, and NaBH4 uses the coccoid of purity min.98% (woods pure pharmaceutical worker already make).LiBH4 uses the purity min.90% coccoid of (with the pure pharmaceutical worker's industry of light), and KBH4 uses the coccoid of purity not clear (pure pharmaceutical worker already makes with light).Do not have to specify that then PEG use molecular weight is the powder of 1.3 ten thousand (Sanyo changes into industry).The calculating of the composition among the embodiment etc. all is that the purity of these hydrogen compounds of supposition all is 100%.And, do not have to specify that the meaning of % is expression quality %.
Embodiment 1
With the 10g molecular weight is that 20,000 laminar PEG puts into aluminum dish, and it is carried on the hot-plate (surface temperature is about 125 ℃) heating and melting.Stir fused PEG with spoon on one side, Yi Bian add the test portion CaH2 powder of specified amount, and dispersed with stirring.After being uniformly dispersed, take off aluminum dish, and be cooled to room temperature (after, abbreviate this preparation method as the fusion entrapping method) from hot-plate.With embedding should solidify the CaH2 powder PEG piece pulverize, and form the granular form of 1～5mm diameter.So said, the addition of CaH2 is changed into 100mg (as hydrogen generating agent A.The content that feeds intake of CaH2 is 1%), 500mg is (as hydrogen generating agent B.The content that feeds intake of CaH2 is 5%), prepare 2 kinds of hydrogen generating agents.
Embodiment 2
The 90ml purified water is packed in the Glass Containers, and the side adds prepared hydrogen generating agent A among the embodiment 1 of specified amount from it, adds a cover immediately then.Hydrogen generating agent gently generates bubble (hydrogen) on the water surface, in several minutes, dissolve simultaneously.In order to compare, in the PET of 1.5L bottle, to take by weighing the CaH2 powder of specified amount, and, add a cover to wherein injecting the 1.5L purified water rapidly.At this moment, when injecting purified water, CaH2 powder and water sharply react, and observation CaH2 powder disperses to airborne appearance in the PET bottle.
Measure so ORP, the pH of the reductive water of preparation, and result's summary is shown in table 1.In addition, in order to compare easily, the addition of CaH2 is scaled the addition of every 1L purified water, under the situation of hydrogen generating agent, with its be scaled interpolation CaH2 amount and represent (that is, when adding 1g hydrogen generating agent A, CaH2 is 10mg).Can know that from table 1 situation of hydrogen generating agent A (CaH2:111mg) is compared with the situation of directly adding CaH2 (133mg), just greatly reduces ORP with a spot of addition.
[table 1]
The addition of table 1 hydrolith and ORP, pH (purified water)
Embodiment 3
The 2L tap water is packed in the 2LPET bottle, and from the upper space of the bottle prepared hydrogen generating agent B the embodiment 1 of specified amount that packs into, then covered and enclosed immediately.Hydrogen generating agent B floats on the water surface and generates bubble, in several minutes, dissolves simultaneously.Measure ORP, the pH of this tap water, result and table 1 are put in order equally and summarized be shown in table 2.
[table 2]
The addition of table 2 hydrolith and ORP, pH (tap water)
Embodiment 4
Preparing pH through dissolved carbon dioxide gas in purified water is 4.20 Soda Ash Light 99.2min..This Soda Ash Light 99.2min. of 450ml is filled in the 500ml PET bottle, and drops into the prepared hydrogen generating agent B in embodiment 1 of specified amount, airtight.Hydrogen generating agent is fierce to generate bubble, and in several minutes, dissolves.The ORP of the reductive water of gained and pH summary are shown in table 3.In addition, the addition of CaH2 is the liquid of 100mg, and the lime carbonate that generated of dissolving and produce some white opacities fully is in the liquid of 200mg at the addition of CaH2, in the bottle bottom small amount of precipitate white opacity thing.Other liquid is water white.
[table 3]
The addition of table 3 hydrolith and ORP, pH (Soda Ash Light 99.2min.)
Embodiment 5
Preparation has the astringent of following composition.
The composition of astringent
Glycerine 2.5%
Glucosyl trehalose 1.2
Trehalose 1.0
Serine 1.0
Xitix sulfuric acid 2Na 1.0
Hydrolysis hydrogenation starch 0.8
Methyl paraben 0.1
The purified water surplus
Because the pH of this astringent is 5.77, therefore add the aqueous citric acid solution of several milliliters 0.1 (mol/l), adjustment pH to 4.13.The adjusted astringent of 100g pH is packed in the Glass Containers, and in astringent, add the prepared hydrogen generating agent B in embodiment 1 of specified amount, airtight.Hydrogen generating agent generates bubble on one side, Yi Bian in several minutes, dissolve.Measure the pH and the ORP of the astringent after dissolving, and the result is shown in table 4.
[table 4]
The addition of table 4 hydrogen generating agent B and ORP, pH (astringent)
Embodiment 6
The gel flush coat agent that preparation has following composition and dissolved dioxide gas.
The composition of Liniment
Methylcellulose gum 3.0%
Glycerine 2.5
Glucosyl trehalose 1.2
Serine 1.0
Raffinose 1.0
Xitix sulfuric acid 2Na 0.8
Hydrolysis hydrogenation starch 0.8
XG 550 0.3
Dioxide gas 0.15
Methyl paraben 0.1
The purified water surplus
The viscosity of this gel is 160dPas (20 ℃), and ORP, pH are 471mV, 4.88.This gel of 100g is packed in the beaker, and add 0.2g the hydrogen generating agent B of preparation among the embodiment 1 is crushed to particle diameter is the Powdered part below the 1mm, fully stir with spoon, make its dissolving.After about 10 minutes, measure the ORP and the pH of this gel, ORP is 27mV, and pH is 6.08.
Embodiment 7
Adjustment has with embodiment 6 same compositions and the flush coat gel manufacturing of having dissolved dioxide gas uses stoste.This stoste is 5dPas 25 ℃ viscosity, and the methylcellulose gum of tackifier is not for dissolving the dispersive state.Prepare the aluminium lamination bag, the powder of the hydrogen generating agent B that in embodiment 6, prepares of the specified amount of packing into therein, stoste is used in the manufacturing of side's injection 25g gel from it, and airtight with hot enclosuring device.Sack is at room temperature placed half a day approximately, and with the top kneading of hand from bag, the mixed dissolution content was preserved for 1 night in refrigerator then.Therebetween, the methylcellulose gum dissolving in the stoste, tackify, and form the dioxide gas dissolving gel that viscosity is the reductibility of 160dPas (20 ℃).In table 5, ORP, the pH of the addition of summary demonstration hydrogen generating agent B and the gel of gained.
[table 5]
The addition of table 5 hydrogen generating agent B and ORP, pH (gel)
Embodiment 8
Prepare by the formed hydrogen generating agent D that forms of PEG/ SODIUM SULPHATE ANHYDROUS 99PCT/LiH=10g/10g/0.2g through the fusion entrapping method.This hydrogen generating agent obtains with the state that the powder of the powder of sodium sulfate and LiH is embedded among the PEG.In 500ml PET, collect the 500ml purified water, and in the upper space weighing of bottle and add the hydrogen generating agent of specified amount, airtight.Hydrogen generating agent is submerged when beginning, but floating to the water surface when hydrogen generates, and in several minutes, dissolves.Measure ORP, the pH of the water after dissolving, and result's summary is shown in table 6.In addition, the amount of the LiH of interpolation is scaled 1L water and representes.
[table 6]
The addition of table 6 hydrogen generating agent D and ORP, pH (purified water)
Embodiment 9
The acid of specified amount is added into forms, and contain hydrogen generating agent E, the F of acid through the preparation of fusion entrapping method by PEG/CaH2=10g/0.5g is formed.These hydrogen generating agents obtain with the state that powdered acid and CaH2 are embedded among the PEG.E contains Citric anhydride as acid, and F contains the L-xitix.In 500ml PET bottle, collect the 500ml tap water, the weighing hydrogen generating agent also is added on wherein, makes the addition of CaH2 be 50mg, and is airtight.Each hydrogen generating agent several minutes with interior generation hydrogen, simultaneously the dissolving.The ORP of the reductive water of gained, pH, and the result of not acidiferous hydrogen generating agent B summary is shown in table 7.Because it is very low to be added with the ORP of hydrogen generating agent of L-xitix, when therefore in being determined at purified water, only dissolving ORP and the pH of the aqueous solution of L-xitix of 0.5g/L, be respectively 495mv, 3.30.This value is the value on the straight line that concerns that is positioned at the ORP that uses hydrochloric acid or caustic alkali to change purified water pH and measure and pH.
[table 7]
The ORP of table 7 hydrogen generating agent E, F and pH (tap water)
Embodiment 10
The acid of specified amount is added into forms, and contain hydrogen generating agent G, the H of acid through the preparation of fusion entrapping method by PEG/LiH=10g/0.19g is formed.G contains Citric anhydride as acid, and H contains the L-xitix.In the 500mlPET bottle, collect the 500ml tap water, the weighing hydrogen generating agent also is added on wherein, makes the addition of LiH be 19mg, and is airtight.Each hydrogen generating agent several minutes with interior generation hydrogen, simultaneously the dissolving.The ORP of the reductive water of gained, pH, and comprise that result's summary of not acidiferous hydrogen generating agent D is shown in table 8.
[table 8]
The ORP of table 8 hydrogen generating agent G, H and pH (tap water)
Embodiment 11
Prepare by the formed hydrogen generating agent of forming of PEG/CaH2=10g/0.5g through the fusion entrapping method.Pulverize blocky hydrogen generating agent, form powder shaped.This powder of weighing 1.05g (CaH2 content: 50mg) with powdery Citric anhydride and the L-xitix of specified amount, in beaker with spoonful mixing.With the mixed powder of the gained internal diameter of stainless steel with bottom of packing into is in the cylindric cylinder of 16mm, and in cylinder, inserts the stainless steel piston that has with the roughly the same external diameter of cylinder internal diameter.It is installed in the oil press device, and 5 tons/cm2 of pressurization is shaped to columned tablet with mixed powder on piston.
Same with embodiment 10, tablet shape hydrogen generating agent J, K, the L of moulding like this is fed in the PET bottle that the 500ml tap water is housed.This tablet the time sinks in the water in beginning, but dissolving constantly carries out, and when the generation of hydrogen became fierceness, it is floating to need several minutes until the dissolving completion to the water surface.Measure ORP, the pH of the reductive water after dissolving, and result's summary is shown in table 9.
[table 9]
The ORP of table 9 tablet shape hydrogen generating agent and pH (tap water)
Embodiment 12
Prepare by PEG/MgH2=10g/0.313g and formed hydrogen generating agent Mg-1, the Mg-2 that forms of PEG/MgH2/ succsinic acid=10g/0.313g/1.40g through the fusion entrapping method.The block hydrogen generating agent Mg-1 of sampling 1.03g, the Mg-2 (MgH2 that contains 31.3mg) of 1.17g in the 500mlPET bottle of packing into, and inject the 500ml purified water, and be airtight.Observe each hydrogen generating agent and dissolve on one side, on one side the slow hydrogen that generates.After hydrogen generates and stops, measure ORP, the pH of purified water, Mg-1 is 43mv, 10.87, and Mg-2 is 32mv, 5.19.
Embodiment 13
With the CaH2 of 125mg, as sodium hydrogencarbonate (8.0g) and fumaric acid (6.45g), powder or granulous water-soluble polymer (2.4g) uniform mixing of the generation dioxide gas of water-soluble cpds.Same with embodiment 11, to this mixture extrusion forming, the hydrogen generating agent of preparation tablet shape, and process bath shampoo.But, under the situation of bath shampoo, use cylindric cylinder and the piston of internal diameter as 28mm.In order to compare, use sodium hydrogencarbonate (8.0g) and fumaric acid (6.1g), moulding does not likewise contain the carbonic acid gas bath shampoo (carbonic acid bath shampoo) of CaH2.
20L is adjusted to 40 ℃ tap water packs in the plastic tank, and drop into above-mentioned bath shampoo, bath shampoo is precipitated to the bottom of bucket, generates micro-bubble and dissolving.After the bath shampoo dissolving finished (foaming stops), the sampling bath water was also measured its pH and ORP.In table 10, show in the lump with carbonic acid bath shampoo relatively measuring the result.In addition, the CaH2 amount in the bath shampoo is equivalent to the concentration of 6.25 (mg/L) with respect to bath water.And the pH of the tap water before bath shampoo adds is 6.91, and ORP is 828mv.According to this result, but the hydrogen generating agent of knowledge capital invention can effectively be used as the reductibility bath shampoo.
[table 10]
The characteristic of table 10 reductibility bath shampoo
Annotate 1) molecular weight=20,000
Annotate 2) annotate 2) the manufacturing 400cP of Wako Pure Chemical Industries, Ltd.
Annotate 3) Japanese VAM & POVAL manufactured marque JP-05
Embodiment 14
Prepare by the formed hydrogen generating agent of forming of PEG/ SODIUM SULPHATE ANHYDROUS 99PCT/CaH2=4g/6g/0.2g through the fusion entrapping method, and as bath shampoo.Use tap water, in bathtub, adjust 150L, 42 ℃ warm water, and in this warm water, drop into 4 aforementioned bath shampoos (with 1 bisection, add up to 8, the concentration with respect to bath water of CaH2 is 5.3mg/L).Bath shampoo sinks to bath base, generates the small quantity of hydrogen bubble, dissolving in about 6 minutes simultaneously.
After the dissolving of bath shampoo finishes, measure the pH and the ORP of bath water immediately, and result's summary is shown in table 11.Measure lasting about 3.5 hours, and 3 adult mans have carried out bathing therebetween.ORP kept reductibility, but pH has reduced some along with the degree of people's bathing almost not changing during this period of time.
[table 11]
The characteristic of table 11 bath shampoo
Embodiment 15
In the molten mass of PEG, will mix by forming of PEG/ SODIUM SULPHATE ANHYDROUS 99PCT/sodium tetraborate/yellow soda ash/CaH2=18g/5g/10.1g/5.3g/1.0g of formed mixture.This mixture is injected mold cylindraceous, and cooling curing prepares alkaline bath shampoo (fusion entrapping method).Sodium tetraborate and yellow soda ash add as the pH adjustment agent of alkalescence.
With this bath shampoo drop into home-use bathtub (42 ℃ tap water, 140L) in the time, generate bubble on one side, dissolving in 5 minutes on one side, and in the centre 3 minutes halfs float to the water surface.In the 500mlPET bottle, collect the bath water of bath shampoo dissolving front and back, measure ORP, the pH of this water next day.The result is described below.
Before the input: ORP=401, pH=6.55
Drop into the back: ORP=161, pH=9.91
Embodiment 16
Prepare by PEG/NaBH4 (abbreviating SBH as)=18g/2g and formed hydrogen generating agent SA and the SB that forms of 19.8g/0.2g through the fusion entrapping method.Here, be that PEG is packed in the ceramic ware, and on hot-plate heating and melting to 90～100 ℃, add and mix SBH, carry out embedding.Dioxide gas is dissolved in the purified water, obtains Soda Ash Light 99.2min. (PH=4.48).At room temperature (about 20 ℃) are added into the above-mentioned hydrogen generating agent of specified amount among this Soda Ash Light 99.2min. 20L respectively, measure the rise time (dissolution time of hydrogen generating agent) of hydrogen, pH, the ORP of the Soda Ash Light 99.2min. after the interpolation.Result's summary is shown in table 12.When being added into the SBH powder in the Soda Ash Light 99.2min. in order to compare, generate hydrogen, and meanwhile several seconds with interior dissolving.
[table 12]
The characteristic of table 12 hydrogen generating agent (SBH class, fusion entrapping method)
Embodiment 17
Likewise prepare by the PEG/SBH/ acid formed following hydrogen generating agent of forming (SC-SF) with embodiment 16 through the fusion entrapping method.Be fed in the 20L purified water (20 ℃) these hydrogen generating agents of specified amount and embodiment 16 likewise estimates hydrogen rise time, pH, ORP.The characteristic summary of hydrogen generating agent is shown in table 13.
1) hydrogen generating agent SC:PEG/SBH/ fumaric acid=14.9g/2g/3.1g
2) SD: the same=194.9g/2g/3.1g
3) SE:PEG/SBH/L-xitix=28.7g/2g/9.3g
4) SF: the same=38.9g/0.2g/0.9g
[table 13]
The characteristic of table 13 hydrogen generating agent (adding the SBH class of acid, the fusion entrapping method)
Embodiment 18
Replace the hydrogen generating agent (SG-SJ) of PEG through the preparation of fusion entrapping method with Xylitol as the following composition of fusion embedding medium.Melt mix temperature is adjusted at 80～110 ℃ scope according to the viscosity of mixed system.
1) SG: Xylitol/SBH/ fumaric acid=14.9g/2.0g/3.1g
2) SH: the same=19.5g/0.2g/0.31g
3) SI: Xylitol/SBH/ thionamic acid/SODIUM SULPHATE ANHYDROUS 99PCT=15.3g/0.2g/0.5g/4g
4) SJ: Xylitol/SBH/ boron oxide/SODIUM SULPHATE ANHYDROUS 99PCT=14g/0.2g/1.9g/4g
For hydrogen generating agent SG, SH, in 20 ℃ purified water 20L,, in 40 ℃ tap water 20L, add the hydrogen generating agent of specified amount for hydrogen generating agent SI, SJ, estimate its characteristic, and the result is summarized in table 14.
[table 14]
The characteristic of table 14 hydrogen generating agent (adding the SBH class of acid, the fusion entrapping method)
Embodiment 19
The powdered mixture of following composition is mixed in beaker.Using and anchor clamps that embodiment 13 is same, is the tablet shape with this mixture forming in pressure forming machine, processes hydrogen generating agent (SK-SN).Likewise measure the characteristic of these hydrogen generating agents with embodiment 17, and the result is summarized in table 15.
1) hydrogen generating agent SK:PEG/SBH/ Hydrocerol A=14.6g/2g/3.4g
2) SL: the same=19.5g/0.2g/0.3g
3) SM: Sorbitol Powder/SBH/ thionamic acid=13g/2g/5g
4) SN: the same=19.3g/0.2g/0.5g
[table 15]
The characteristic of table 15 hydrogen generating agent (adding the SBH class of acid, extrusion forming method)
Embodiment 20
Hydrogen generating agent SC, the SD that respectively 10g, 50g is adjusted in embodiment 17 is fed in the home-use bathtub (150L tap water, 42 ℃), estimates ORP, pH, the hydrogen rise time t of the bath water after dissolving.The ORP=651mv of barren tap water, pH=7.24, when dropping into hydrogen generating agent SC: ORP=-16mv, pH=6.96, t=1.1 minute, when dropping into SD: ORP=-103mv, pH=7.08, t=4.2 minute.
Embodiment 21
Following one-tenth is grouped into is dissolved in the purified water, and further dissolved carbon dioxide gas, weakly acidic beauty liquid processed.
The composition of beauty liquid
Glycerine 3.0%
Pyrrolidone carboxylic acid-Na 2.5
Sweet Lay alkali 1.5
Xitix-PMG 1.0
Vitamin PP 1.0
Collagen 0.5
Aloe extract 0.2
Argy wormwood extract 0.2
Methyl paraben 0.2
Mucinase-Na 0.1
XG 550 0.07
Potenlini-2K 0.05
The Soda Ash Light 99.2min. surplus
Will be in embodiment 16 prepared hydrogen generating agent SA0.1g, SB1.0g is added in this beauty liquid of 1kg, makes its dissolving, processes the beauty liquid of reductibility.The ORP of the beauty liquid before hydrogen generating agent adds is 611mv, and pH is 4.68, and the ORP of the beauty liquid after the interpolation, pH are in the situation of hydrogen generating agent SA: ORP=-6mv, pH=4.75, SB:ORP=-88mv, pH=4.91.
Embodiment 22
Will with the SBH of 50mg, as the sodium hydrogencarbonate (8.0g) of the generation dioxide gas of water-soluble cpds and fumaric acid (6.18g), in embodiment 13 used powder or granulous water-soluble polymer (3.5g) uniform mixing.Same with embodiment 13, to this mixture extrusion forming, the hydrogen generating agent of preparation tablet shape, and form bath shampoo.In order to compare, use sodium hydrogencarbonate (8.0g) and fumaric acid (6.1g), same moulding does not contain the dioxide gas bath shampoo (carbonic acid bath shampoo) of SBH.
20L is adjusted to 40 ℃ tap water packs in the plastic tank, and drop into above-mentioned bath shampoo, bath shampoo is sink to the bottom of bucket, generates micro-bubble and dissolving.The bath shampoo dissolving is got the bath water sample and is measured its pH and ORP after finishing (foaming stops).In table 16, show in the lump with carbonic acid bath shampoo relatively measuring the result.In addition, SBH measures with respect to bath water, is equivalent to the concentration of 2.5 (mg/L).And the pH of the tap water before bath shampoo adds is 7.16, and ORP is 632mv.
[table 16]
The characteristic of table 16 reductibility bath shampoo (SBH class, extrusion forming method)
Embodiment 23
Likewise prepare by the formed hydrogen generating agent of forming of Sorbitol Powder/SBH/ L-glutamic acid/SODIUM SULPHATE ANHYDROUS 99PCT=15.4g/0.2g/0.4g/4g with embodiment 13 through extrusion forming method.This hydrogen generating agent of 5g is fed in 40 ℃ of tap water of 20L ORP, the pH of the tap water after mensuration hydrogen rise time t, the dissolving.The result is ORP=21mv, pH=6.02, t=6.8 minute.
Embodiment 24
Use LiBH4, SBH, KBH4 likewise to have the mixture of following composition, process the hydrogen generating agent of tablet shape through the extrusion forming method moulding as hydroboration metal-salt and embodiment 13.
1) PEG/LiBH4/ succsinic acid/SODIUM SULPHATE ANHYDROUS 99PCT=5g/0.5g/1.42g/3.5g
2) PEG/SBH/ succsinic acid/SODIUM SULPHATE ANHYDROUS 99PCT=5g/0.5g/0.82g/3.5g
3) PEG/KBH4/ succsinic acid/SODIUM SULPHATE ANHYDROUS 99PCT=5g/0.5g/0.57g/3.5g
The various hydrogen generating agents of specified amount are added in 42 ℃ of tap water of 20L ORP, the pH of the tap water after mensuration hydrogen rise time, the hydrogen generating agent dissolving.Result's summary is shown in table 17.
[table 17]
The characteristic of table 17 hydrogen generating agent (various hydrogen compounds, extrusion forming method)
Embodiment 25
The hydrogen generating agent that contains the following composition of LiH, CaH2, MgH2, SBH through the preparation of fusion entrapping method.
1) PEG/LiH/ SODIUM SULPHATE ANHYDROUS 99PCT=10g/0.2g/6g
2) PEG/CaH2/ SODIUM SULPHATE ANHYDROUS 99PCT=10g/0.5g/6g
3) PEG/MgH2/ succsinic acid/SODIUM SULPHATE ANHYDROUS 99PCT=10g/0.31g/1.4g/6g
4) PEG/SBH (1)/succsinic acid/SODIUM SULPHATE ANHYDROUS 99PCT=10g/0.25g/0.41g/6g
In addition, the hydrogen generating agent that contains SBH through the following composition of extrusion forming method moulding.
5) PEG/SBH (2)/succsinic acid=12.8g/0.2g/0.33g
In the hydrogen generating agent that has added succsinic acid, the addition of succsinic acid be in and with the reaction of water in the amount of the alkali that generates.The accurate blocky hydrogen generating agent of the about 1g of weighing, and in the 500ml PET bottle with the relief outlet of its pack into the inlet that possesses water and gas.To bottle, inject the 50ml purified water from the inlet of water, and the H2 gas that generates is collected in the graduated cylinder of filling water from gas discharge outlet, measure this gas vol.In addition, after hydrogen generates end, measure pH, the ORP of the purified water in the PET bottle.The result summarizes and to be shown in table 18, the hydrogen growing amount that every 1g hydrogen generating agent is generated, be with according to the almost approaching value of the desired theoretical amount of the reaction formula of each hydrogen compound and water.
[table 18]
Table 18 generates the quantitative of hydrogen by hydrogen generating agent
Embodiment 26
Use kibbler to pulverize embodiment 25, and be the sieve of 0.75mm, obtain powder through mesh through the prepared blocky hydrogen generating agent that contains MgH2, SBH (1) of fusion entrapping method.The hydrogen generating agent of powder shaped that likewise will be equivalent to MgH2, the SBH (1) of 50mg with embodiment 25 is packed in the PET bottle of 500ml, and injects the 100ml purified water, measure and reaction times of water, and the hydrogen growing amount.In order to compare, the powder of weighing 50mg test portion MgH2, SBH is likewise measured hydrogen growing amount etc.
But the water that in the experiment of using test portion, uses is in the purified water of injecting, to add the succsinic acid of the alkali aequum of neutralization generation, the sour water that is modulated into.The pH of this water is 2.95 (situation of MgH2), 3.20 (situation of SBH).Result's summary is shown in table 19.According to this result, can know under the MgH2 situation, if use hydrogen generating agent of the present invention, then can accomplish reaction in the time that test portion is direct and the sour water reaction is shorter than making.In addition, during the weighing test portion, hydrogen generating agent, test portion MgH2 are dryness, and it is handled easily, but because test portion SBH is hygroscopic, so difficult treatment.
[table 19]
The reaction times of the Powdered hydrogen generating agent of table 19, test portion and water and hydrogen growing amount
Applicability in the industry
Can be dissolved in owing to hydrogen generating agent of the present invention in the waterborne compositions such as astringent, bath shampoo, beverage and give reductibility, therefore be used as skincare product or heath food.In addition, owing to generating highly purified hydrogen, therefore be used to fuel that fuel cell uses etc. with water reaction.
Claims (8)
1. hydrogen generating agent, it is that at least a pulverous hydrogen compound fusion of being selected from hydrogenated alkali metal, hydrogenation alkaline-earth metal, hydroboration metal-salt is embedded in the hydrogen generating agent that forms in water-soluble cpds or their mixture of solid-like,
Said fusion embedding is, the crystallinity water-soluble cpds that will have fusing point is heated to and makes its fusion more than the fusing point, adds the hydrogen compound powder and also mixes, and makes it be dispersed in the molten mass cooling curing.
2. hydrogen generating agent as claimed in claim 1, wherein, water-soluble cpds is a macromolecular compound.
3. hydrogen generating agent as claimed in claim 2, wherein, macromolecular compound is a polyoxyethylene glycol.
4. hydrogen generating agent as claimed in claim 1, it forms in the mixture of water-soluble cpds, containing acid.
5. hydrogen generating agent as claimed in claim 1, it is shaped to the tablet shape.
6. a bath shampoo is characterized in that, contains each described hydrogen generating agent of claim 1～4.
7. reductive water or reductibility waterborne compositions, it is dissolved in water or the waterborne compositions through each the described hydrogen generating agent with claim 1～5 and forms.
8. a method for forming hydrogen is characterized in that, generates hydrogen through making the reaction of each described hydrogen generating agent of claim 1～5 and water or waterborne compositions.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP325659/2005 | 2005-11-10 | ||
| JP2005325659 | 2005-11-10 | ||
| JP2005358411 | 2005-12-13 | ||
| JP358411/2005 | 2005-12-13 | ||
| JP2006130653 | 2006-05-09 | ||
| JP130653/2006 | 2006-05-09 | ||
| JP2006161833 | 2006-06-12 | ||
| JP161833/2006 | 2006-06-12 | ||
| PCT/JP2006/321944 WO2007055146A1 (en) | 2005-11-10 | 2006-11-02 | Hydrogen-generating agent and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101304943A CN101304943A (en) | 2008-11-12 |
| CN101304943B true CN101304943B (en) | 2012-06-27 |
Family
ID=38023151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800416646A Expired - Fee Related CN101304943B (en) | 2005-11-10 | 2006-11-02 | Hydrogen generating agent and use thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20080292541A1 (en) |
| JP (1) | JP4384227B2 (en) |
| KR (1) | KR100990010B1 (en) |
| CN (1) | CN101304943B (en) |
| WO (1) | WO2007055146A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20080292541A1 (en) | 2008-11-27 |
| KR100990010B1 (en) | 2010-10-26 |
| JPWO2007055146A1 (en) | 2009-04-30 |
| WO2007055146A1 (en) | 2007-05-18 |
| KR20080066088A (en) | 2008-07-15 |
| JP4384227B2 (en) | 2009-12-16 |
| CN101304943A (en) | 2008-11-12 |
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